Fibers and fabrics coated with an alkyl phosphite-polyolefin wax adduct and process therefor



United States Patent FIBERS AND FABRICS COATED WITH AN ALKYLPHOSPHITE-POLYOLEFIN WAX ADDUCT AND PROCESS THEREFOR Isaac J. Levine,East Brunswick, and Arthur K. Ingberman, Somerville, N.J., assignors toUnion Carbide Corporation, a corporation of New York No Drawing.Continuation-impart of applications Ser.

Nos. 469,840 and 469,890, July 6, 1965. This application June 28, 1966,Ser. No. 561,005

U.S. Cl. 117-1395 11 Claims Int. Cl. C08j 1/44 ABSTRACT OF THEDISCLOSURE Textile fibers and fabrics are coated with a finishing agentcomprising an alkyl phosphite-polyolefin wax adduct. In the process, thecoated fibers and fabrics are subjected to a post heating step.

This application is a continuation-in-part of copending applicationsSer. No. 469,840, filed July 6, 1965 and Ser. No. 469,890, filed July 6,1965.

This invention relates to the finishing of fiber and articles made fromfibers such as textiles. More particularly, the invention relates tonovel finishing agents for fibers and textiles.

Fibers useful herein can be classified as natural, semisynthetic,synthetic or glass fibers and include natural organic fibers comprisingessentially cellulosic fibers (from vegetable sources) such as cotton,hemp, flax (linen), ramie, sisal, jute and the like; polymeric naturalorganic fibers e.g. proteinaceous fibers (from animal sources) such assilk (produced from the moth of the Bombyx species), wool and the like;polymeric semi-synthetic organic fibers comprising rayons or cellulosederivatives made from wood pulp or cotton linters such as regeneratedcellulose rayons such as viscose rayon and cuprammonium rayon, celluloseesters such as acetate rayon and cellulose ethers such as ethylcellulose; polymeric synthetic organic fibers e.g., nylons (polyamides),polyesters (reaction product of polybasic acids and glycols)polyethylene, polypropylene, vinyl chloride/vinyl acetate copolymer,vinyl chloride/acrylonitrile copolymer polyacrylonitrile, vinylchloride/vinylidene chloride copolymer, polyurethanes and the like; andglass fibers such as Fiberglas.

Finishing herein refers to treatment of fibers either per se or as atextile or fabric to impart new characteristics and properties such ashandle, appearance, drape, touch (surface lubricity, flexibility,compressibility and elastic recovery), softness, sheen, durability,shrink resistance, proofing against crushing, slip, water and moths.

Cationic salts of simple primary amines such as hexadecyl aminehydroacetate, salts of simple tertiary amines such as hexadecyl dimethylamine hydroacetate, quaternary ammonium salts such as hexadecyl dimethylbenzyl ammonium chloride, salts of amino acids such as monostearoyldiethylene triamine dihydroacetate, quaternary ammonium salts of aminoamides such as fi-diethyl aminoethylstearamide ethosulfate, salts ofimidazolines such as ,u-heptadecyl, N-aminoethyl imidazolinedihydroacetate, quaternary derivatives of imidazolines, salts of aminoesters such as B-dihydroxyethyl amine stearatehydroacetate andquaternary ammonium salts of amino esters have heretofore been used asfinishing agents. Practically all materials that are in commercial useare derivated from stearic acid. Hydrocarbon chains of greater lengthhave been sought but high cost and poor availability have barred theirgeneral use despite promising experimental results.

Heretofore, modified polyolefin waxes have been prepared by oxidation orby adducting polyolefin waxes with polar compounds such as maleicanhydride, thioglycolic acid, and the like. Oxidation, however, is arandom reaction that produces a variety of products that are usuallyundesirably colored and have objectionable odors. Adduction with polarcompounds also suffers from serious drawbacks. For example, theadduction with maleic anhydride is a very high temperature reaction thatrequires long heating times leading to some decomposition of the maleicanhydride. Moreover, during the reaction some of the molecules are madelonger by copolymerization and oxidative cross-linking. Afteremulsification, there is a tendency toward instability and breaking ofthe emulsion or creaming. While many of the problems met with maleicanhydride are obviated through the use of thioglycolic acid, the highcost and unpleasant odor of this acid render its adducts with polyolefinwaxes unsuitable for commercial use.

It has also been proposed to produce a modified polyethylene wax bythermally degrading a high molecular weight linear polyethylene at atemperature of from to 400 C. in the presence of an organic phosphite toform an addition product having an average molecular weight of from 200to 4000. However, there are several drawbacks to this approach and theproducts produced thereby. For example, the thermal degradation of highmolecular weight linear polyethylene in the presence of an organicphosphite requires impractically long reaction times and causes theorganic phosphite, which is markedly unstable at polyethylene thermaldegradation temperatures, to decompose to phosphine and relatedby-products, which are malodorous and toxic. Kosolapoff,Organophosphorus Compounds, John Wiley & Sons, Inc., New York, (1950),p. 182. Moreover, the product produced is undesirably colored and whileemulsifiable yields a poorly colored emulsion.

It is an object, therefore, of the present invention to providefinishing agents of relatively very great molecular weight for improvingthe tear strength, edgewear resistance, needle burn resistance and flexabrasion resistance of fibers. It is another object to provide textileand fabrics having improved handle. It is another object to increase thewater repellency of textiles and fabrics, especially of proteinaceousand cellulosic fiber textiles.

A fiber finishing agent has not been discovered comprising an alkylphosphite modified polyolefin wax. Textiles and fabrics having improvedtear strength, edgewear resistance, needle burn resistance and flexabrasion resistance are obtained by treating the textile with an alkylphosphite modified polyolefin wax. It has also been found that thesemodified waxes also overcome the problems heretofore associated withmodified polyolefin waxes.

The term polyolefin is used herein to denote normally solid homopolymersof alpha monoolefinically un-- saturated hydrocarbons as well asnormally solids copolymers thereof. Suitable polyolefins includepolyethylene, polypropylene, polyethylene-polypropylene copolymers andthe like. Polyolefin waxes useful in this invention have an average ofat least one-half, and preferably one, olefinic double bond per polymermolecule and a molecular weight of from about 1000 to about 5000.Polyolefin waxes typically contain at least one type of olefinic doublebond and sometimes a combination of two or three different types ofdouble bonds. A polyolefin wax molecule containing an olefinic doublebond can be represented by the formula RRflhCHR wherein R is an alkylgroup and R and R each are hydrogen or an alkyl group. Where R and R areboth 0 hydrogen, the bond is termed a terminal vinyl type of doublebond. Where R is hydrogen and R is an alkyl group, the bond is termed avinylidene type of double bond and wherein R is hydrogen and R is analkyl group, the bond is termed an internal type of double bond. All ofthese types of olefinic double bonds are capable of entering into anaddition reaction with organic compounds of the class described herein.

Polyolefin waxes can be prepared by the pyrolysis or thermal degradationof higher molecular weight polyolefin polymers or by the directpolymerization of an olefin monomer or monomers to a wax of desiredmolecular weight. Pyrolysis, for example, can be carried out in a heatedpyrolysis tube at about 450 to 600 C. Linear, high density polyethylenewaxes having a density of 0.94 and above are preferred. Polyethylenewaxes having lower densities, as well as other polyolefin waxes can alsobe employed.

Polyolefin wax adducts useful in this invention are prepared byadducting at least about 25 percent, preferably about 50 percent, of theolefinic double bonds in the polyolefin wax with an alkyl phosphitehaving at least one hydrogen atom capable of entering into an additionreaction with an olefinic double bond.

Suitable alkyl phosphites that can be reacted with polyolefin waxes toform an adduct thereof can be represented by the formula II H-P-O Rswherein X represents an oxygen of a sulfur atom, R is an alkyl grouphaving from 1 to 16 carbon atoms and A is hydrogen or -OR wherein R isan alkyl group having from 1 to 16 carbon atoms. Thus as used herein,the term phosphite refers to both phosphites and thiophosphites. Itshould be understood that when A is -OR R and R, can be the same ordifferent alkyl groups. Suitable alkyl phosphites include methyldihydrogen phosphite, ethyl dihydrogen phosphite, nbutyl dihydrogenphosphite, n-heptyl dihydrogen phosphite, n-hexadecyl dihydrogenphosphite, dirnethyl hydrogen phosphite, diethyl hydrogen phosphite,dipropyl hydrogen phosphite, di-n-butyl hydrogen phosphite, din-octylhydrogen phosphite, di-n-pentadecyl hydrogen phosphite, methyl ethylhydrogen phosphite, ethyl-ndecyl hydrogen phosphite, methyl dihydrogenthiophosphite, ethyl dihydrogen thiophosphite, n-undecyl dihydrogenthiophosphite, dimethyl hydrogen thiophosphite, diethyl hydrogenthiophosphite, di-n-butyl hydrogen thiophosphite, di-n-heptyl hydrogenthiophosphite, di-nhexadecyl hydrogen thiophosphite and the like.Inasmuch as the alkyl thiophosphites produce a modified polyolefin waxhaving a typical mercaptan odor, and the alkyl dihydrogen phosphites canunder certain condition lead to crosslinking, the dialkyl hydrogenphosphites are preferred for purposes of this invention. These preferredphosphites have the formula wherein R and R are as defined above. Itshould be noted that trialkyl phosphites are not suitable reactants inthis invention because they do not have a hydrogen atom available toenter into a free radical addition reaction with the olefinic doublebond present in polyolefin waxes. For a detailed discussion of themechanism of the free radical addition reaction between alkyl phosphitesof the class described herein and the olefinic double bond, reference ismade to Stacey et al., Organic Reactions, 13, 218-225, John Wiley andSons, Inc., New York (1963).

The polyolefin wax adducts described herein can be prepared by blendingthe polyolefin wax and alkyl phosphite, in the liquid phase, for examplein the melt or in solution, and reacting them in the presence of anaddition reaction initiator with agitation at a temperature of fromabout C. to about 200 0, preferably from about C. to about C. Blendingand agitation can be carried out in any manner which insures intimateadmixing of the reactants and good heat transfer throughout the reactionmass during the reaction time.

If the addition reaction is conducted in solution, the reaction mediumshould be a liquid organic solvent inert with respect to the reactantsunder the reaction conditions and which is a solvent for the polyolefinwax and alkyl phosphate. Suitable solvents include benzene, toluene,xylene, cyclohexane, methylcyclohexane, isooctane, and the like, andhalogenated hydrocarbon sol vents such as chlorobenzene,orthodichlorobenzene, 1,1,2-trichloroethane, bromobenzene,a-chloronaphthalene and the like. It is preferred to use only as muchsolvent as will completely dissolve the polyolefin wax and alkylphosphite.

It is preferred to conduct the addition reaction in the melt by heatingthe polyolefin wax to its melting point and above and blending in thealkyl phosphite.

Generally an excess over the amount of alkyl phosphite theoreticallynecessary to react with the olefinic double bonds present in thepolyolefin wax molecules should be used in order to achieve good ratesof reaction and to insure complete reaction. A high reaction rate is notnecessarily the sole factor in determining the optimum amount of alkylphosphite to be used. For example, it is only required that about 25percent, preferably 50 percent, or above of the olefinic double bonds beadducted to provide an ultimately emulsifiable product. Thus, the use ofmore alkyl phosphite than is required is unnecessary except to reducethe time needed to conduct the addition reaction.

The addition reaction between the polyolefin wax and the alkyl phosphitecan be initiated by organic peroxides, organic azo compounds,ultraviolet radiation, and X-radiation. Stacey et al., supra, p. 219.Suitable organic peroxide initiators or catalysts include di-t-butylperoxide, 2,5 dimethyl 2,5-di(t-butyl peroxy) hexyne-S, dicumylperoxide, benzoyl peroxide, lauroyl peroxide, and the like. Suitableorganic azo compounds include azonitriles such as azo-bis-butyronitrileand the like. In using ultraviolet radiation as the initiator, aphotosensitizer such as benzophenone should be present.

The addition reaction between an olefinic double bond and an alkylphosphite, and the adduct formed can be shown as follows:

wherein A, R and X are as defined previously. As indicated above thereactive olefinic double bond in the polyolefin wax molecule can be aterminal, vinylidene, or internal type of double bond. The additionproduct is termed a phosphonate ester of a polyolefin wax which asindicated above, includes thiophosphonate esters.

Polyolefin wax-alkyl phosphite adducts while emulsi fiable under certaincircumstances, can be rendered readily emulsifiable in one of two ways:(1) by converting at least about 25 percent, and preferably about 50percent of the oxyalkyl groups attached to phosphorus atoms in theadduct to hydroxyl groups, for example 1'; l l Z wherein A, R, and X areas defined previously, or (2) by reacting the phosphonate ester groupsof the polyolefin wax-alkyl phosphite adduct with an amine having atleast one reaction amino hydrogen atom.

The conversion of the oxyalkyl groups in the polyolefin wax-alkylphosphite adduct to hydroxyl groups can be accomplished by acidhydrolysis, base hydrolysis or pyrolysis, and the converted product canbe termed a modified polyolefin wax-alkyl phosphite adduct.

Hydrolysis can be carried out in a solvent for the polyolefin wax-alkylphosphite adduct or in the heated wax adduct itself. Acid hydrolysis canbe accomplished using monovalent acids such as hydrochloric acid,chloroacetic acid, and the like. Polyvalent acids such as sulfuric acid,phosphoric acid, and the like can be used to hydrolyze but the saltby-products must be washed out before emulsification. Basic hydrolysiscan be accomplished using bases such as alkyl metal hydroxide such aspotassium hydroxide, sodium hydroxide, and the like and aqueous ammoniaand the like. It should be understood that basic hydrolysis produces asalt which itself is readily emulsifiable, Thus as used herein thephrase hydroxyl groups is intended to include the salts thereof as well.

A preferred method for converting the oxyalkyl groups to hydroxy groupsis by pyrolysis. Pyrolysis is carried out either in batch orcontinuously in suitable apparatus at a temperature of from about 280 C.to about 475 C. for a period of time sufficient to accomplish theaforementioned degree of conversion. It has been found that a methylphosphite modified polyolefin wax will not undergo pyrolysis and thiswax adduct must be hydrolyzed to convert the oxymethyl groups tohydroxyl groups. The pyrolysis method of conversion is preferred becauseit provides for a high conversion rate, uses low cost equipment, doesnot require a catalyst, and does not require an additional reagents asin hydrolysis thus eliminating blending problems. The by-product of thepyrolysis reaction is the alkene corresponding to the R or R alkylgroup.

The reaction product of a polyolefin wax-alkyl phosphite adduct and anamine can be termed an amine modified polyolefin wax-alkyl phosphiteadduct. Suitable amines can be represented by the formula wherein Rrepresents a monovalent organic radical having from 1 to 12 carbonatoms, R represents hydrogen or a monovalent organic radical having from1 to 12 carbon atoms, and R and R when interconnected, represent aheterocyclic ring. The phrase monovalent organic radica refers tounsubstituted radicals as Well as to sub stituted radicals. Exemplary ofsuch monovalent radicals are the following: alkyl radicals, such asmethyl, ethyl, n-propyl, n-butyl, n-hexyl, 2-ethyl-n-hexyl, n-octyl,n-dodecyl, and the like; cycloalkyl radicals, such as cyclohexyl and thelike; unsaturated aliphatic and cycloaliphatic radicals, such as allyl,cyclopentenyl, and the like; halogenated alkyl and cycloalkyl radicals,such as chloroethyl, bromoethyl, fluoroethyl, 2-chloro-n-propyl,2-bromo-n-propyl, 2-chloro-n-butyl, 3-chlor0-n-amyl, 3-bromon-amyl, 2chloro-n hexyl, Z-chlorocyclohexyl, and the like; alkoxy and aryloxysubstituted alkyl and cycloalkyl radicals, such as methoxymethyl,ethoxyethyl, 3-ethoxyn propyl, 4-ethoxy-n-butyl, 3-ethoxy 2ethyl-n-hexyl 2 methoxycyclohexyl, phenoxymethyl, 2 phenoxyethyl,3-phenoxy-n-propyl, 2 phenoxycyclohexyl, and the like; hydroxysubstituted alkyl and cycloalkyl radicals; tertiary amino substitutedalkyl and cycloalkyl radicals; aralkyl radicals, such as benzyl,2-phenylethyl, B-phenyl-n-propyl, l-phenyl-n-butyl, l-phenyl-n-dodecyl,and the like; aryl radicals, such as phenyl, naphthyl, and the like;halogenated aryl radicals, such as p-chlorophenyl, pbromophenyl,p-fluorophenyl, p-iodophenyl, 2-chloronaphthyl, 2-bromonaphthyl, and thelike; alkoxy and aryloxy substituted aryl radicals, such asp-methoxyphenyl, p-ethoxyphenyl, p-n-propoxyphenyl, and the like;hydroxy substituted aryl radicals; tertiary amino substituted arylradicals; alkaryl radicals, such as o-methylphenyl, p-ethylphenyl,p-n-dodecylphenyl, p-( 2 ethyl n hexyl)phenyl, and the like; nitrosubstituted aryl radicals such as p-nitrophenyl, Z-nitronaphthyl, andthe like.

Illustrative of suitable amines where R is a monovalent radical and R ishydrogen or a monovalent radical are methylamine, ethylamine,n-butylamine, n-octylamine, dimethylamine, diethylamine,ethyl-n-propylamine, di n butylamine, allylamine, cyclohexylamine,cyclopentylamine, ethoxyethylamine, Z-bromo-n-propylarnine,3-ethoxy-2-ethyl n hexylamine, 2-hydroxyethylamine,Z-hydroxypropylamine, Z-arnino-l-butanol,3-(N,N-di-nbutylamino)propylamine, Z-phenylethylarnine,l-phenyl-nbutylamine, aniline, m-toluidine, 2,3-xylidine, mesidine,l-naphthylamine, N-methylaniline, 4-(N,N-diethylamino) aniline, 4chloroaniline, 2 chloro 1 naphthylamine, 4 methoxyaniline, 4ethoxyaniline, 4 hydroxyaniline, 4-nitroaniline, N-propylallylamine,N-phenylbenzylamine, N cyclohexylheptylamine, 3 (aminomethyl)pyridine,1-naphthalenemethylamine, 2-pyrenamine, and the like. Illustrative ofsuitable amines where R and R together form a heterocyclic ring arepyrrole, Z-methylpyrrole, 3-ethylpyrrole, and the like.

Polyolefin wax-alkyl phosphite adducts can be reacted with an amineeither in solution or in the melt at temperatures of from about 150 toabout 300 C. for a period of time to react at least 25%, preferably 50%,of the wax phosphonate ester groups with the amine. Generally about astoichiometric amount of amine is employed but readily emulsifiableproducts can be obtained using less than stoichiometric amounts. Incalculating the stoichiometry, one phosphonate ester group is presumedto react with one amino hydrogen atom. It is preferred to conduct thereaction in the absence of oxygen to secure a white product.

From the foregoing it should be evident that polyolefin wax adductsuseful in this invention fall into the following groups: (1) adducts ofpolyolefin waxes and an alkyl phosphite; (2) polyolefin wax-alkylphosphite adducts having at least about 25 percent of the oxyalkylgroups attached to phosphorus atoms converted to hydroxyl groups and (3)amine modified polyolefin wax-alkyl phosphite adducts. Groups (2) and(3) are preferred because of their case of emulsifiability as comparedto group (1).

The application of the phosphite modified wax to fibers or textiles canbe readily accomplished by use of a hot melt or solution of the wax androller coating, dip coating, spray coating or otherwise.

Alternatively, and advantageously, the limitations of hot melt orsolution application or incorporation can be avoided by use of ananionic, cationic or non-ionic emulsion of the phosphite modified wax asthe coating mixture. Typically water emulsions are prepared by meltingtogether the alkyl phosphite modified polyolefin wax and a fatty acidsuch as, for example, propionic, butyric, valeric, caproic, enanthylic,caprylic, capric, lauric, tridecoic, myristic, pentadecanoic, palmitic,megaric, stearic, nondecylic, arachidic, behenic, carnaubic, hyenic,carborceric, cerotic, laccroic, melissic, montanic, psyllic, acrylic,crotonic, iso-crotonic, vinylacetic, methylacrylic, tiglic, angelic,senecioic, hexenic, oleic, elaidic, erucic, brassidic, propiolic,propynoic, terolic, 2-butynoic, pentinoic, 2-pentinoic, amylpropiolic,palrnitotic, stearolic, behenolic, sorbic, linoleic and linolinic acids.These acids have the general formula wherein n is an integer from 0 to32 and x is an odd number from 5 to +1 with the proviso that when n=0,x=+l. An amine soap is then added such as monoand triethanolamine,monoisopropanolamine, diisopropanolamine, triisopropanolamine,morpholine, N,N-dimethylethanolamine and N,N-diethylethanolamine. Themixture is stirred until thoroughly mixed or until it becomes clear.Other emulsifying aids such as polymeric glycols and ethoxylated soybeanoils can also be used depending on whether an anionic, cationic ornon-ionic emulsion system is desired. Water which has been heated toabout C. is added and the mass stirred under pressure. The mixture isthen vigorously agitated in a suitable device, e.g., a bladed mixer,colloid mill or other shear producing apparatus to form the emulsion. Analkyl phosphite modified polyolefin wax solids content of from 0.1 to 25percent is preferred in emulsions to be used as finishing agents.

The water emulsion of the modified wax is easily coated onto the fibersubstrate by any of the conventional techniques including brushing,dipping, spraying, roller coating and the like. The water of theemulsion is evaporated either by allowing the coated-on emulsion tostand at room temperature or preferably by force drying as by airmovement around and/or application of heat to the emulsion coating. Upondrying there remains a nontacky and non-blocking coating which impartsimproved handle, lubricity and abrasion resistance to fibers.

Generally from about 0.01 to about 25% by weight of modified wax basedon the fabric weight is coated onto the fabric. Preferred amounts arebetween 0.1 and 10% by weight on the same basis.

After application of the alkyl phosphite modified polyolefin wax to thefiber substrate, it is preferred to subject the coated substrate to apost-heating step, particularly by heating to a temperature above themelting point of the wax provided the fiber is not degraded thereby.This enables a greater degree of flow of the wax into the interstices ofthe fabric and facilitates reaction of the reactive groups of the waxwith 'hydroxyl groups or acetate groups on cellulosic fibers such ascotton or rayon.

As mentioned above, the finishing of textile fibers improves the waterrepellency characteristics. Other aids can be simultaneously employedincluding N-octadecyl-N- ethylene urea, alkyl isocyanates, thiocyanates,organosilicon compounds, aluminum oxides and soaps, copper soaps,chromium soaps, zirconium soaps and oxide, organo-halosilanes, rareearth metal soaps, petroleum and vegetable waxes, methylol stearamide,pyridium chlorides. Flameproofing agents can also be combined withphosphite modified polyolefin wax prior to application to the textilefibers such as boric acid/borax mixtures, ferric hydroxide, antimonyoxychloride, stannic oxide hydrated, titanic hydroxide, bismuth trioxidehydrated, zinc stannate, aluminum borate, lead peroxide, ceriumlhydroxide, aluminum hydroxide, chromic hydroxide, silica hydrated,aluminum silicate, magnesium silicate and magnesium ammonium phosphateand with these pentachlorodiphenyl, neoprene, chlorinated parafiin,vinyl chloride resins and aniline hydrochloride.

Other flameproofing agents include volatile phosphates and sulfamates.Mothproofing agents and mildewcides too can be applied with thefinishing agent such as inorganic fluorides,dichlorobenzene-sulfon-methylamide, p-aminobenzenesulfonamide,dichlorodiphenyl trichloroethane (DDT), pentachlorophenol and the sodiumsalt of pentachlorodihydroxy triphenylmethanesulfonic acid. Alsorotproofing agents such as copper salts of rosin and tall oil, terpinolhydrate as well as alkalies, formaldehyde, dyes, pigments, sequestrants,dispersants, starch, dextrin, glue, gums, china clay, Epsom salts,glycerol, soaps, soluble oil, antichlors, antifoaming and antistaticagents, batching oils, enzymes, lubricants, rust preventatives, spottingand weighting aids.

The present invention is illustrated by the following examples. Allparts and percentages are by weight unless otherwise stated.

PREPARATION OF ALKYL PHOSPHITE MODIFIED POLYOLEFIN WAXES EXAMPLES 1-5Example 1 Into a 500 ml. flask equipped with a stirrer, thermometer,condenser and dropping funnel is placed 200 grams of polyethylene waxprepared by pyrolyzing at 480 C. polyethylene having a density of 0.96and a melt index (ASTM D-l238-57T) of 5. The wax has a number averagemolecular weight of 2000 and contains an average of one olefinic doublebond per polymer molecule, over percent of which are terminal vinylgroups. 200 ml. of chlorobenzene and 40 grams of diethyl hydrogenphosphite are added to the wax in the flask and the reaction mass isheated to reflux at 169 C. A solution of 1 gram of2,5-dimethyl-2,5-di-(t-butoxy)-hexyne-3 initiator is added over aboutthree minutes and the reaction mass is refluxed for four hours.Thereafter chlorobenzene and excess diethyl hydrogen phosphite areremoved by vacuum distillation. The polyethylene wax-phosphite adduct isallowed to cool. The amount of reaction is determined by measuring thechange in the vinyl double bond absorption of 11.02;. in the infraredand is found to be percent. The product is a hard, white wax withabsorptions in the infrared at 8.00114, 8.59 9.44 and 9.67;.4characteristic of an alkyl phosphonate ester.

Example 2 In an Erlenmeyer flask, g. of the phosphite adduct describedin Example 1 is dissolved in 250 ml. of refluxing chlorobenzene and asolution of 7 g. of KOH in methanol is added. The mixture is boiled for10 minutes and then poured into a large volume of cold methanol. Theinfrared spectrum of the precipitated product shows the 800a band tohave shifted to 835 and the doublet at 9.44; and 9.67,u to have shiftedto 930p and 9.39 indicating that hydrolysis has occurred.

Example 3 One hundred grams of phosphite adduct prepared in Example 1 ispyrolyzed by heating under a nitrogen stream to 340 C. Gas evolutionbegins at about 280 C. and becomes more vigorous as the temperatureincreases. The wax is cooled rapidly. The infrared spectrum shows theoriginal 8.00; phosphoryl absorption band to have shifted to 8.5a.

Example 4 A mixture of g. of the phosphonate ester was prepared inExample 1 and 30 ml. of N,N-di-n-butyl-1,3- propane diamine are heatedwith stirring under nitrogen for 1 hour in a 500 ml. flask equipped witha stirrer, thermometer, condenser and gas inlet tube. The molten wax ispoured into a large volume of acetone and the precipitated productfiltered, washed with acetone, and dried. The infrared spectrum of theproduct shows all of the original phosphonate ester bands shifted. Forexample, the phosphoryl absorption at 8.00 1. is shifted to 8.45 Achemical analysis indicates that two moles of amine are reacted.

Example 5 Example 4 is duplicated using 20 g. of aniline. The infraredspectrum of the product indicates complete reaction.

Example 6 One hundred grams of the modified wax of Example 2 is mixedwith 20 grams of morpholine, 20 grams of oleic acid and 800 grams ofwater. The mixture is charged to a pressure reaction vessel and heatedto 150 C. with agitation and immediately cooled. There is obtained awhite emulsion having a solids content of 14.7%.

The above emulsion is diluted to 10 percent by weight polyethylene wax.A piece of rayon triacetate fabric is immersed in the emulsion. Onesection of the fabric is air dried and then heated for one minute at 350F. A second section is only air dried. Both sections are well coatedwith an adherent covering of the modified wax. The heat-treated fabricis smoother and had better handle. Puncture of the post-treated fabricwith a needle does not break the threads. Both sections of fabric arewaterproof.

Example 7 Several emulsions of the modified wax of Example 4 areprepared as in Example 1 and diluted to solids contents of 2.5, 5, and10%. Squares of cotton fabric are immersed in each of these emulsions.One-half of each square is air dried for two hours at room temperature.The other half of each square is oven dried at 130 C. for 45 minutes.The post-treated fabric is water resistant, with applied water ballingup.

While not necessary, post-heat treatment of coated fabric at 60-137 C.for 1 to 60 minutes provides a superior product in terms of tearstrength, edgewear resistance, needle burn resistance and flex abrasionresistance. Heat-treated fabrics retain these properties, includingwater-proofness, after laundering.

Examples 8-9 Flex abrasion Example Solids on fabric resistance (cyclesto failure) 8 0. 3 1, 550 9 0. 3 2, 527 Control I. 656 Control II. 0. 3864 C ontrol III 0 395 Control IV 0. 3 763 Example Strips of fiber glasscloth (No. 181 weave, type 2967 finish), 4" x 8", are immersed inemulsions of the modifield polyethylene wax of Example 5. Emulsionsolids content and immersion conditions are adjusted such that the clothpicks up 0.5, 1.0, 2.5, 5.0 and 10.0 wt. percent solids. The clothsamples are squeezed partly dry, then air dried at room temperature. Thesamples of dried cloth are heat treated at 140 C. for 10 minutes in anair oven to fuse the polyethylene wax coating.

After treatment the samples are examined visually and by feel toqualitatively rate the softness. The fabric stilfness is quantitativelyrated also by the blending length test for fabrics (ASTM-1488-55T).

The fiber glass cloth sample treated with 0.5 wt. percent solids from acationic or anionic emulsion is significantly improved in softness,hand, or drape properties.

The modified polyethylene wax coating functions as a lubricant andpermits slippage at fiber interfaces. The results show that the 0.5%emulsion solids level gives the softest fabric, and the fabric becomesstiffer at higher levels.

As indicated above not only are cellulosic fibers such as cotton andrayon improved in the present invention but proteinaceous substratessuch as wool are also improved. As an illustration, the application of a2% by weight emulsion of the modified wax of Example 2 onto a woolencloth imparts needle burn resistance and improved handle.

Synthetic fibers can also be improved particularly in handle byapplication of the modified wax in accordance with the presentinvention. Thus, polypropylene, nylon, and polyester fabrics can beimproved in edgewear resistance',"needle burn resistance and durabilityby the ap plication of modified wax coatings.

What is claimed is:

1. Textile fiber having a coating thereon of from 0.01 to about 25percent by weight, based on the weight of said fiber, of a finishingagent comprising an adduct selected from the group consisting of (1) anadduct of an alpha mono-olefinically unsaturated hydrocarbon homopolymeror copolymer wax having an average of at least about one-half of anolefinic double band per polymer molecule and a molecular-weight ofabout 1000 to about 5000 and an alkyl phosphite having from 1 to 32carbon atoms inclusive and at least one hydrogen atom capable ofentering into an addition reaction with an olefinic double bond, atleast about 25 percent of said double bonds being adducted with saidalkyl phosphite, (2) an adduct of said wax and said alkyl phosphitewherein at least about 25 percent of the oxyalkyl groups containing from1 to 32 carbon atoms inclusive attached to phosphorus atoms areconverted to hydroxyl groups, and (3) an adduct of said wax and saidalkyl phosphite containing phosphonate ester groups wherein at leastabout 25 percent of said phosphonate ester groups are reacted with anamine having at least one reactive amino hydrogen atom.

2. Fiber of claim 1 wherein the wax is a polyethylene wax.

3. Fiber claimed in claim 2 wherein said alkyl phosphite has the formulawherein X represents an atom selected from the group consisting ofoxygen and sulfur, R is an alkyl group having from 1 to 16 carbon atomsinclusive, and A is selected from the group of hydrogen and OR.; whereinR is an alkyl group having from 1 to 16 carbon atoms.

4. Fiber of claim 3 wherein said fiber is organic.

5. Fiber of claim 3 wherein said fiber is glass.

6. Fabric comprising textile fibers having a coating thereon of fromabout 0.01 to about 25 percent by weight, based on the weight of saidfabric, of a finishing agent comprising an adduct selected from thegroup consisting of (1) an adduct of an alpha mono-olefinicallyunsaturated hydrocarbon homopolymer or copolymer wax having an averageof at least about one-half of an olefinic double bond per polymermolecule and .a molecular weight of about 1000 to about 5000 and analkyl phosphite having from 1 to 32 carbon atoms inclusive and at leastone hydrogen atom capable of entering into an addition reaction with anolefinic double bond, at least about 25 percent of said double bondsbeing adducted with said alkyl phosphite (2) an adduct of said wax andsaid alkyl phosphite wherein at least about 25 percent of the oxyalkylgroups containing from 1 to 32 carbon atoms inclusive attached tophosphorus atoms are converted to hydroxyl groups, and (3) an adduct ofsaid wax and said alkyl phosphite containing phosphonate ester groupswherein at least about 25 percent of said phosphonate ester groups arereacted with an amine having at least one reactive amino hydrogen atom.

7. Fabric of claim 6 wherein said fabric comprises organic fibers.

8. Fabric of claim 6 wherein said fabric comprises glass fibers.

9. Fabric claimed in claim 6 wherein said alkyl phosphite has theformula wherein X represents an atom of the group of oxygen and sulfur,R is an alkyl group having from 1 to 16 carbon atoms inclusive, and A isselected from the group of hydrogen and -OR wherein R is an alkyl grouphaving from 1 to 16 carbon atoms.

10. Method for treating textile fibers comprising applying to suchfibers an adduct selected from the group consisting of (1) an adduct ofan alpha mono-olefinically unsaturated hydrocarbon homopolymer orcopolymer wax having an average of at least about one-half of anolefinic double bond per polymer molecule and a molecular weight ofabout 1000 to about 5000 and an alkyl phosphite having from 1 to 32carbon atoms inclusive and at least one hydrogen atom capable ofentering into an addition reaction with an olefinic double bond, atleast about 25 percent of said double bonds being adducted with saidalkyl phosphite (2) an adduct of said wax and said alkyl phosphitewherein at least about 25 percent of the oxyalkyl groups containing from1 to 32 carbon atoms inclusive attached to phosphorus atoms areconverted to hydroxyl groups, and (3) an adduct of said wax and saidalkyl phosphite containing phosphonate ester groups wherein at leastabout 25 percent of said phosphonate ester groups are reacted with anamine having at least one References Cited UNITED STATES PATENTS1,715,855 6/1929 McBerty 117-1395 1,803,936 5/1931 Frielaender 117-13951,819,241 8/1931 Hirschberger 117--139.5

WILLIAM D. MARTIN, Primary Examiner.

THEODORE G. DAVIS, Assistant Examiner.

U.S.Cl.X.R.

